1261075 玖、發明說明： 發明所屬之技術領域 — 本發明係有關使用脈衝逆電解，從酸性溶液中沉積銅於 ' 裝飾性基材上’以製備更爲均勻分布之鍍銅層。 先前技術 從酸性溶液中電鍍銅爲眾所周知，有許多工業上的應 用。在多數的應用上，係將被鍍物置於電極，此種技術而後 - 稱爲架式電鑛。 - 這些應用中之其中一種爲電鍍鋁合金汽車輪圈，此鋁合♦鲁 金表面在浸鍍於鋅酸鹽溶液前需淸潔及去脂，留下一薄鍍鋅 層於合金表面。因爲銅電鍍溶液之酸性性質，鋅酸鹽膜在浸 鍍時會被破壞，爲避免鋅酸鹽膜之破壞，一般正常下係於鋅 · 酸鹽膜上施以輕度酸浴以電鍍一層薄鍍鎳層，再從高酸性溶 ·- 液中於鍍鎳層上沉積銅。鋅酸鹽/鎳之處理可促進電鍍銅至 - 銘合金基材上’因爲銅無法直接電鍍。在此銘合金汽車輪圏 之特殊實例中，常習慣鍍上一層相對厚銅膜，因在電鍍最終 鎳及鉻飾面之前，通常需將銅膜拋光。 __ 銅沉積有兩個目的：（1 )其具有調平性質，因此可將鑄 造鋁輪圈的缺陷隱藏起來，以及（2 )其較軟且易於拋光。銅 表面之拋光可產生一平坦光面，在施行最終飾面後，看起來 較具吸引力。此外，拋光表面延展軟銅能有效地封住銅鍍層 上的孔洞，可提升鍍層之抗腐蝕性。 現今技術其中一項的缺點爲必須鍍著最小厚度之銅於 . 鋁基上，以確保在拋光程序時銅沉積沒有被完全移除，並且 . 1261075 在後續製程階段提供鋁適當的保護。然而，由於使用在酸性 銅電鍍階段之電極及添加劑的本質，鍍銅層的分布一般係不 均勻的。爲於凹陷處達到所需之最小厚度，輪圈之曝露區會 有額外的銅鍍著其上，對於電鍍者而言，這是非常浪費及耗 、 費成本的。 . 另一銅沉積之應用爲電鍍於塑膠基材上，其在汽車工業 上非常普遍。通常於這些應用，塑膠基材先經前處理以允許 ~ 其接受由無電方式電鍍之薄鎳沉積。一旦薄鎳層使得塑膠構 · 件成爲導電時，在施加最終鎳及鉻飾面之前使用一相當的銅 層。最小銅厚度通常由電鍍零件之最後使用者所指定，例如 汽車製造者。由於傳統裝飾性電解之銅金屬沉積分布狀態不 佳，爲於複雜元件之凹陷處達到最小銅厚度，導致曝露區之 _ 鍍銅過量。再者，對電鍍者產生浪費銅，亦會導致如沉積突 — 枝或燃燒之其他問題，或由於尺寸精度的失誤而遭退件。突 枝及燃燒對於這些習於電鍍技藝係眾所周知之熟悉項目’且 這類缺點在電鍍沉積中會發生於電鍍物件之曝露區。 因此對於一可提供大幅改善鍍件表面之鍍層分布性的製11# 程將是有益的。藉由降低需達到最低厚度銅之製程時間以提 高產量。此外，其能減少銅耗量，且亦可減少因尺寸誤差、 銅沉積燃燒或突枝導致退件的可能性。 ' 其他具有更均勻分布之銅沉積的應用係爲有益亦是本 發明所意圖的。 使用從酸性溶液沉積銅之脈衝逆電解技術’其係使用在 從酸性溶液中電鍍銅至印刷電路板及其他基材之電子產業 ~ 是眾所周知的。美國專利Ν 0.6，3 1 9，3 8 4，Ta y 1 〇 r等人’該標 · 1261075 的在此全部倂入本案以作爲參考資料，其揭露將銅電沉積在 半導體基材上之方法，其中該酸性銅鍍浴實質上缺乏光亮性 及/或調平性。 使用在電子應用上之添加劑的基本化學，以及其在脈衝 - 逆電流電鍍狀態相較於直流電狀態之性質，係由T. P e a 1* S ο η · 戶斤角军釋 5 NN Effect of Pulsed Current On The Electrodeposition of Chromium and Copper 〃，PhD 論文，安思通大學（Aston U n i v e r s i t y)，英國，1 9 8 9 ,該標的在此全部倂入本案以作爲 · 參考資料。添加劑大致類似該等使用於此一般架式電鍍之應•肇 用且槪括包含磺基丙基硫及聚乙二醇結合氯離子作用。脈衝 逆電流及這些添加劑的使用產生電化學效應，導致金屬分布 的提升。此效應促使電鍍銅進入電路板之孔洞中，這些孔洞 、 一般直徑約〇 . 5 mm及深度2〜3 mm，這些孔洞的有效電流 - 密度極低，且在如電鍍合金鋼圈之一般架式電鍍應用的正常 範圍之外。 不幸的，此分布效應可能會被其他添加劑所破壞。因爲 這原因，應用於印刷電路板之電鍍浴組成一般非常簡單且無♦馨 法提供一全亮及調平銅沉積。相反的，在一般架式電鍍應用 上，銅沉積的表面是最重要的。因爲不使用脈衝電鍍’更調 ' 平及光亮之添加劑效果在此分布效應上就不重要了。 應用於電子方面之電解液基本組成，與使用在傳統架式 電鍍是不同的。一般來說，使用於電子/線路板之電鍍浴含 有75 g/Ι之硫酸銅五水合物、1 1 5 ml/1之濃縮硫酸、40 mg/1 之氯離子及專屬之添加劑（一種低金屬/高酸浴）°反過來 說，用於一般架式電鍍之電鍍浴含有 2 2 0 g/Ι之硫酸銅五 、 1261075 水合物、3 5 m 1 /1之濃縮硫酸、8 0 m g /1之氯離子及專屬之添 加劑（一種高金屬/低酸浴）。 本發明者很驚訝的發現，脈衝逆電流電鍍技術於印刷電 路板之應用，在包括上述之鋁合金汽車輪圈及塑膠基材之一 -般架式電鍍之電鍍銅時，有很好的表現。意外的是，該電流 -密度範圍非常不同於印刷電路板之應用。本發明者發現脈衝 逆電流電鍍使用於一般架式電鍍相較於傳統電鍍浴其物件 鍍著最低厚度之各種應用時，可產生較少之銅損耗。 - 當利用脈衝逆電鍍結合電子型式電解組成電鍍合金輪®# 圈時，以及一種可使脈衝逆電解最佳之添加劑系統，可導致 輪圈上的銅沉積分布大幅提升。這對電鍍者而言，有二個明 顯好處：（1 )較少之多餘銅沉積產生在輪圈的曝露區，以及 (2 )輪圈之凹陷處在與前述應用相比可於較短時間下鍍上 ^ 最少厚度，因而增加生產量。 就本發明者所能知道的而言，該技術之前並沒有提出或 使用在傳統架式電鍍廠，可能是因爲使用脈衝逆電流導致被 鍍物件之鍍層於高電流密度區變得灰暗。然而，在合金汽車Φφ 輪圈的案例裡，一般銅沉積還要拋光處理，使得該負面效應 不再是個要素。或者，電鑛銅之階段可含有一段之脈衝逆電 解，繼之施以一段直流電電解，以留下較只施加脈衝逆電解 光亮之最終沉積。 此外，使用脈衝逆電解電鍍物件之低電流密度區在使用 適當之專屬添加劑時可保有一明亮之表面，因而在全物件留 下光亮表面。 1261075 因此下列所陳述之實例，脈衝逆電流技術完全適用在各 種應用，其中更爲均勻分布之銅沉積是可預期的，例如電鍍 一最小厚度之規格，如合金輪圈或電鍍汽車用塑膠零件。 發明內容 使用脈衝逆電鍍沉積銅係一種在酸性銅電鍍浴中電鍍 裝飾性物件之方法，其包含之步驟有： (a )懸置一裝飾性物件於一含有銅離子、配對離子及氯 離子之電鍍浴中；與 (b )利用脈衝逆電流電鍍該裝飾性物質一段時間，以在 該裝飾性物質至少一處之表面產生所欲厚度之 銅。 在較佳實施例中，酸性銅電鍍浴更包含聚醚及二價硫化 合物。 實施方式 本發明於利用脈衝逆電流在酸性銅電鍍浴中電鍍銅於 裝飾性物件，以在裝飾性物件表面鍍上所欲厚度之銅。本發 明特別適用於在鋁合金輪圈及汽車用塑膠零件上電鍍更爲 均勻厚度的銅。 本發明之酸性銅鍍浴一般包含銅離子、配對離子源及氯 離子。其他有助於提升銅鍍層之添加劑亦可加於浴中。 存在於電鍍浴中之銅離子，其濃度約1 0 g/ι至50 g/ι 。硫酸銅五水合物係爲一種銅化合物，其對本發明之 浴是有用的，雖然其他銅化合物亦見之於文獻中。電鍍浴 .-般含硫酸銅五水合物之濃度約在50 g/l至1 00 g/Ι，以約 1261075 例中，伴隨著鋼嵌板（P a n e 1 )之赫耳電池試驗（H u 1 1 c e 1 1 t e s t) 係爲了利用X射線螢光技術來量測銅鍍層厚度。爲避免鋼嵌 板浸鍍上銅沉積，嵌板在轉移至赫耳電池之前需先透過氰化 物銅溶液鍍上一層最低厚度之銅（將近〇. 1 - 0.2 # m)。所有 的赫耳電池試驗利用〃 s u 1 i'a s t v施行於2 5 °C。 脈衝電流機制爲1 〇 m s陰極，0 . 5 m s陽極，對印刷電 路板應用來說，其爲正常脈衝機制。 實例1 - 5係說明習知技藝及顯示現行酸性銅電鍍之電 流技術。使用於這些實例之組成及電鍍條件列於下方表1。 I# 表1.酸性銅電鍍條件習知技藝 實例1 實例2 實例3 實例4 實例5 硫酸銅五水合物 210 g/1 210 g/1 75 g/1 75 g/1 75 g/1 硫酸 32 m)/l 32 ml/1 115 ml/1 115 ml/1 115 ml/1 氯離"f* 85 mg/1 85 mg/1 85 mg/1 85 mg/1 75 mg/1 添加劑 Cumae 8000SL Cumae 8000SL Cumae 8000SL Cumae 8000SL 300 mg/1 PAG1 添加劑 30 mg/1 disodium salt2 電鍍型式 直流ΐι 逆脈衝 直流電 逆脈衝 直流電 電流 1安培 1安培 1安培 1安培 1安培 電鍍時間 15分鐘 分鐘 15分鐘 15分鐘 15分鐘 厚度比 6.07 : 1 6.8 ： 1 4.0 ： 1 3.0 ： 1 4.0 : 1 聚乙二醇 2 disodium salt =雙（乙院-2 -硫酸）二硫化物二鈉鹽 實例1 製備一含有2 1 Q g/Ι硫酸銅五水合物、32 ml/ι硫酸及85 mg/1氯離子之溶液。力[:|入專屬添力U齊IJ (Cumae 8 0 0 0 SL，· ·種 用於一般架式酸性銅電鍍之M a c D e r m ! d製程）。赫耳電池嵌 1261075 板以直流電]安培電鍍1 5分鐘。嵌板在點上測量之厚度相 田方 < 主女竜流密度2.0A/dm*·及0.1A/dm2。在2.0A/dni2之厚 度被除以0.1 A/dm2之厚度得到6.07 : 1之厚度比。經過全部 範圍之嵌板表面爲明亮的。 製備如同貫例1之溶液以及將赫耳電池嵌板利用平均電 ^ 1安培及陽極：陰極電流密度將近3 : 1之脈衝逆電流機 制電鍍1 5分鐘。如同之前計算厚度比爲6.8 : 1。嵌板表面 · 在咼電流岔度區爲平滑暗淡的，低電流密度區則爲明亮的。修修 製備一含有75 g/Ι硫酸銅五水合物、丨丨5 mi/丨硫酸，8S g/1氯離子之溶液及Cumac 8000SL添加劑。赫耳電池嵌板 以直流電1安培電鑛1 5分鐘，經計算之厚度比爲4. 〇 :丄。 @過全嵌板之沉積爲完全明亮的。1261075 发明, INSTRUCTION DESCRIPTION: FIELD OF THE INVENTION The present invention relates to the use of pulsed reverse electrolysis to deposit copper from an acidic solution onto a 'decorative substrate' to produce a more evenly distributed copper plated layer. Prior Art Electroplating of copper from acidic solutions is well known and has many industrial applications. In most applications, the object to be plated is placed on the electrode, and this technique is followed by a type of electrowinning. - One of these applications is an galvanized aluminum alloy wheel rim. The surface of the aluminum alloy ♦ Lu Jin should be cleaned and degreased before being immersed in the zincate solution, leaving a thin galvanized layer on the alloy surface. Because of the acidic nature of the copper plating solution, the zincate film will be destroyed during immersion plating. In order to avoid the destruction of the zincate film, it is generally applied to the zinc acid salt film to apply a mild acid bath to plate a thin layer. The nickel layer is plated, and copper is deposited on the nickel plating layer from the highly acidic solution. The treatment of zincate/nickel promotes electroplating of copper to - on alloy substrates. 'Because copper cannot be directly electroplated. In the special case of this alloy car rim, it is customary to apply a relatively thick copper film, because the copper film is usually polished before the final nickel and chrome finish. __ Copper deposits serve two purposes: (1) they have a leveling property, thus hiding the defects of the cast aluminum rim, and (2) they are soft and easy to polish. The polishing of the copper surface produces a flat surface that looks more attractive after the final finish. In addition, the polished surface-expanding soft copper effectively seals the holes in the copper plating and improves the corrosion resistance of the coating. One of the shortcomings of today's technology is that a minimum thickness of copper must be plated on the aluminum base to ensure that the copper deposit is not completely removed during the polishing process, and that 1261075 provides proper protection of the aluminum during subsequent processing stages. However, due to the nature of the electrodes and additives used in the acid copper plating stage, the distribution of the copper plating layer is generally not uniform. In order to achieve the required minimum thickness in the depression, the exposed area of the rim will have additional copper plating thereon, which is very wasteful, costly and costly for the electroplater. Another application for copper deposition is electroplating on plastic substrates, which is very common in the automotive industry. Typically in these applications, the plastic substrate is pretreated to allow it to accept thin nickel deposits that are electrolessly plated. Once the thin nickel layer is made conductive, the equivalent copper layer is applied before the final nickel and chrome finish is applied. The minimum copper thickness is usually specified by the last user of the plated part, such as a car manufacturer. Due to the poor distribution of copper metal deposition in traditional decorative electrolysis, the minimum copper thickness is reached in the depression of complex components, resulting in excessive copper plating in the exposed area. Furthermore, the waste of copper on the electroplater can also lead to other problems such as deposition or branching or burning, due to mistakes in dimensional accuracy. Bursting and burning are well known to those skilled in the electroplating art' and such defects occur in electroplated deposits in the exposed areas of electroplated articles. It would therefore be beneficial to provide a process that would provide a significant improvement in the coating distribution of the surface of the plated part. Increase production by reducing the process time required to achieve the lowest copper thickness. In addition, it reduces copper consumption and also reduces the possibility of returning due to dimensional errors, copper deposits, or spurs. Other applications where a more uniform distribution of copper deposits is beneficial is also contemplated by the present invention. The use of pulsed reverse electrolysis techniques for depositing copper from acidic solutions, which is used in the electronics industry for electroplating copper from acidic solutions to printed circuit boards and other substrates, is well known. U.S. Patent No. 6, </RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Wherein the acid copper plating bath is substantially lacking in glitter and/or leveling properties. The basic chemistry of additives used in electronic applications, as well as the nature of their pulse-to-current galvanic state compared to the dc state, is derived from T. P ea 1* S ο η · 斤角角军 5 NN Effect of Pulsed Current On The Electrodeposition of Chromium and Copper 〃, PhD paper, Aston U niversity, UK, 1 9 8 9 , the subject of which is hereby incorporated into this case as a reference. The additives are substantially similar to those used in this general rack plating and include the inclusion of sulfopropyl sulfide and polyethylene glycol in combination with chloride ions. The pulsed reverse current and the use of these additives produce an electrochemical effect that leads to an increase in metal distribution. This effect causes the electroplated copper to enter the holes in the board. These holes, generally about 5 mm in diameter and 2 to 3 mm in depth, have extremely low effective current-density and are generally in the form of plated alloy steel rings. Outside the normal range of plating applications. Unfortunately, this distribution effect can be destroyed by other additives. For this reason, the composition of the plating bath applied to the printed circuit board is generally very simple and does not provide a full bright and leveling copper deposit. Conversely, copper deposition surfaces are of the utmost importance in general rack plating applications. Because the use of pulse plating does not use the 'flattering' and the bright additive effect is not important in this distribution effect. The basic composition of the electrolyte applied to the electronics is different from that used in conventional rack plating. In general, electroplating baths for electronic/circuit boards contain 75 g/Ι of copper sulfate pentahydrate, 1 15 ml/1 of concentrated sulfuric acid, 40 mg/1 of chloride ion and exclusive additives (a low metal). /High acid bath)° In other words, the plating bath used for general rack plating contains 2 2 0 g/Ι of copper sulfate 5, 1261075 hydrate, 3 5 m 1 /1 concentrated sulfuric acid, 80 mg /1 Chloride and proprietary additives (a high metal / low acid bath). The present inventors have surprisingly found that the application of pulsed reverse current plating technology to printed circuit boards has a good performance in the electroplating of copper including one of the above-mentioned aluminum alloy automobile rims and plastic substrates. . Surprisingly, this current-density range is very different from the application of printed circuit boards. The inventors have found that pulsed reverse current plating can be used in general rack plating to produce less copper loss than in conventional plating baths where the minimum thickness of the article is applied. - When using pulsed reverse plating combined with electronic type electrolysis to form a plating alloy wheel®# ring, and an additive system that optimizes pulsed reverse electrolysis, the copper deposition distribution on the rim is greatly improved. For the electroplater, there are two distinct benefits: (1) less excess copper deposits are produced in the exposed area of the rim, and (2) dents in the rim are shorter in comparison to the aforementioned applications. The bottom is plated with a minimum thickness, thus increasing throughput. As far as the inventors are aware, this technique has not previously been proposed or used in conventional rack plating plants, probably because the use of a pulsed reverse current causes the plating of the object to be plated to become dark in the high current density region. However, in the case of the alloy automobile Φφ rim, the general copper deposition is also polished, so that the negative effect is no longer an element. Alternatively, the stage of the copper ore may contain a period of pulsed reverse electrolysis followed by a period of direct current electrolysis to leave a final deposition that is more counter-electrolytic than the applied pulse. In addition, the low current density region of the electroplated article using pulse reverse electrolysis maintains a bright surface when appropriate proprietary additives are used to leave a shiny surface on the entire object. 1261075 Thus, the pulsed reverse current technique is well suited for a variety of applications, as described in the following examples, where more uniform distribution of copper deposits is expected, such as plating a minimum thickness specification, such as alloy wheels or plastic parts for electroplating automotive applications. SUMMARY OF THE INVENTION The use of pulsed reverse plating to deposit copper is a method of plating a decorative article in an acid copper electroplating bath, comprising the steps of: (a) suspending a decorative article in a copper ion, a counter ion, and a chloride ion. And (b) electroplating the decorative material with a pulsed reverse current for a period of time to produce copper of a desired thickness on at least one surface of the decorative material. In a preferred embodiment, the acid copper electroplating bath further comprises a polyether and a divalent sulfide. Embodiments The present invention utilizes a pulsed reverse current to electroplate copper to a decorative article in an acid copper electroplating bath to plate a desired thickness of copper on the surface of the decorative article. The invention is particularly suitable for electroplating a more uniform thickness of copper on aluminum alloy rims and automotive plastic parts. The acid copper plating bath of the present invention generally comprises copper ions, a counter ion source, and chloride ions. Other additives that help to enhance the copper coating can also be added to the bath. The copper ions present in the electroplating bath have a concentration of about 10 g/ι to 50 g/ι. The copper sulfate pentahydrate is a copper compound which is useful for the bath of the present invention, although other copper compounds are also found in the literature. Electroplating bath. The concentration of copper sulfate-containing pentahydrate is about 50 g/l to 100 g/Ι, in about 12,610,075 cases, accompanied by the steel panel (P ane 1 ) Heric battery test (H u 1 1 ce 1 1 test) In order to measure the thickness of the copper plating by X-ray fluorescence technology. In order to avoid copper deposition on the steel panel immersion plating, the panel is first plated with a minimum thickness of copper (nearly 〇. 1 - 0.2 # m) by transferring the cyanide copper solution before transferring it to the Hertz cell. All Hertz battery tests were performed at 25 °C using s s u 1 i'a s t v. The pulse current mechanism is 1 〇 m s cathode, 0.5 m s anode, which is a normal pulse mechanism for printed circuit board applications. Examples 1 - 5 illustrate conventional techniques and current techniques showing current acid copper plating. The compositions and plating conditions used in these examples are listed in Table 1 below. I# Table 1. Acid Copper Plating Conditions Conventional Techniques Example 1 Example 2 Example 3 Example 4 Example 5 Copper sulfate pentahydrate 210 g / 1 210 g / 1 75 g / 1 75 g / 1 75 g / 1 sulfuric acid 32 m )/l 32 ml/1 115 ml/1 115 ml/1 115 ml/1 Chlorine away"f* 85 mg/1 85 mg/1 85 mg/1 85 mg/1 75 mg/1 Additive Cumae 8000SL Cumae 8000SL Cumae 8000SL Cumae 8000SL 300 mg/1 PAG1 Additive 30 mg/1 disodium salt2 Plating type DC ΐι Reverse pulse DC reverse pulse DC current 1 amp 1 amp 1 amp 1 amp 1 amp plating time 15 minutes minute 15 minutes 15 minutes 15 minutes thickness ratio 6.07 : 1 6.8 : 1 4.0 : 1 3.0 : 1 4.0 : 1 Polyethylene glycol 2 disodium salt = double (Bei-2 - sulfuric acid) disulfide disodium salt Example 1 Preparation of a 2 1 Q g / Ι sulfuric acid A solution of copper pentahydrate, 32 ml/ι sulfuric acid and 85 mg/1 chloride ion. Force [:| into the exclusive force force U Qi IJ (Cumae 8 0 0 0 SL, · · For general shelf type acid copper plating M a c D e r m ! d process). The Hercules battery is embedded with 1261075 plates and galvanized for 15 minutes. The panel is measured at the point of the thickness of the field. The main female turbulent density is 2.0A/dm*· and 0.1A/dm2. The thickness of 2.0 A/dni2 was divided by the thickness of 0.1 A/dm2 to obtain a thickness ratio of 6.07:1. The entire surface of the panel is bright. A solution such as that of Example 1 was prepared and the Hertz cell panel was electroplated for 15 minutes using a pulsed reverse current of approximately 1:1 amp and anode: cathode current density of approximately 3:1. As before, the calculated thickness ratio is 6.8:1. Panel surface · Smooth and dim in the 咼 current 岔 area, bright in the low current density area. Repair A solution containing 75 g/Ι copper sulfate pentahydrate, 丨丨5 mi/丨 sulfuric acid, 8S g/1 chloride ion, and Cumac 8000SL additive was prepared. Hertz battery panel with DC 1 amp of electric ore for 15 minutes, the calculated thickness ratio is 4. 〇 : 丄. The deposition of the @full panel is completely bright.
·· 製備如同實例3之溶液以及將赫耳電池嵌板利用平均電 :L 1安培及陽極：陰極電流密度將近2 : 1之脈衝逆電流機 制電镀1 5分鐘。如同之前計算厚度比爲3 · 〇 : 1。沉積在高 電流密度區爲平滑暗淡的，低電流密度區則爲明亮的。• Prepare a solution as in Example 3 and use the average electricity of the Hertz cell panel: L 1 amp and anode: Cathodic current density is approximately 2:1 pulsed reverse current machine plating for 15 minutes. As before, the calculated thickness ratio is 3 · 〇 : 1. The deposition in the high current density region is smooth and dim, and the low current density region is bright.
次備一白有7 5 g /1硫酸銅五水合物、1 1 5 m 1 /1硫酸及7 5 llg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇及3〇 mg/i 之雙（乙烷-2-硫酸鹽）二硫化物二鈉鹽。赫耳電池嵌板以直流 % 1安培電鍍1 5分鐘，經計算之厚度比爲4. 〇 : I。經過全 1261075 範圍之沉積爲半明亮的。 實例6 - 1 2顯示本發明非限制性電鍍浴。使用於這些實例之 組成及電鍍條件列於下方表2 - 3。 表2 .本發明各種銅電鍍浴 實例6 實例7 實例8 實例9 硫酸銅五水合物 75 g/1 75g/l 75 g/1 75 g/1 硫酸 115 ml/1 115 ml/1 115 ml/1 115 ml/1 氯離子 75 mg/1 75 mg/1 150 mg/1 150 mg/1 添加劑 300 mg/1 PAG MacuSpec PPR 300 mg/1 PAG 300 mg/1 PAG 添加劑 30 mg/1 disodium salt2 30 mg/1 disodium salt3 50 mg/1 disodium salt3 電鑛型式 逆脈衝 逆脈衝 逆脈衝 逆脈衝 電流 1安培 1安培 1安培 1安培 電鍍時間 15分鐘 15分鐘 15分鐘 15分鐘 厚度比 2.20 ： 1 1.9 : 1 2.20 ： 1 2.15 ： 1 〗PAG =聚乙二醇 2 disodium salt =雙（乙院-2 -硫酸）二硫化物二鈉鹽 3 disodium salt =雙（3 -擴丙基）二硫化物二鈉鹽 1261075 表3.本發明各種銅電鍍浴 實例10 實例η 實例12 硫酸銅五 水合物 75g/l 75g/l 75 g/1 硫酸 115 ml/1 115 ml/1 115 ml/1 氯離子 75 mg/l 75 mg/l ]50 mg/l 添加劑 300 mg/l PAG1 300 mg/l PAG 300 mg/l PAG 添加劑 30 mg/l disodium salt2 30 mg/l disodium salt3 30 mg/l disodium salt3 添加劑 40 mg/l調平化合物A 50 mg/l調平化合物B 40 mg/l調平化合物A 電鍍型式 逆脈衝 逆脈衝 逆脈衝 電流 1安培 1安培 1安培 電鍍時間 15分鐘 15分鐘 15分鐘 厚度比 1.70 : 1 2.20 : 1 2.15 ： 1 ·· 聚乙二醇 2 disodium salt =雙（乙院-2 -硫酸）一硫化物—鈉鹽 3 disodium salt =雙（3_擴丙基）—硫化物一納鹽 實例6 製備一含有75 g/Ι硫酸銅五水合物、1 1 5 ml/1硫酸及75 mg/1氯離子之溶液。添加300 mg/1之聚乙二醇及30 mg/1 之雙（乙烷-2 -硫酸鹽）二硫化物二鈉鹽。赫耳電池嵌板利用平 · 均電流1安培及陽極：陰極電流密度將近2 : 1之脈衝逆電 ~ 流機制電鍍1 5分鐘’經計算之厚度比爲2.2 0 ·· 1。嵌板在高 電流密度區爲平滑暗淡的，低電流密度區則爲半明亮的。 實例7 製備一含有75 g/丨硫酸銅五水合物、1 1 5 ml/1硫酸及75 -14- 1261075 mg/l氯離子之溶液。力□入專屬添力Π劑（μ acuSpec PPR，— 種用於印刷電路板電鍍之M a c D e r m i d製程）。赫耳電池嵌板 利用平均電流1安培及陽極：陰極電流密度將近2 : 1之脈 衝逆電流機制電鍍1 5分鐘，經計算之厚度比爲1 .9 : 1。沉 . 積在局電流密度區爲平滑暗淡的，低電流密度區則爲半明亮 · 的。 實例8 * 製備一含有7 5 g /1硫酸銅五水合物、1 1 5 m 1 /1硫酸及1 5 0 mg/1氯離子之溶液。添加3 00mg/l之聚乙二醇及30mg/l之 雙（3-磺丙基）二硫化物二鈉鹽。赫耳電池嵌板利用平均電流 1安培及陽極：陰極電流密度將近2 : 1之脈衝逆電流機制電 鍍15分鐘，經計算之厚度比爲2.20 : 1。沉積在高電流密度 區爲平滑暗淡的，低電流密度區則爲半明亮的。 - 實例9 - 製備一含有75 g/Ι硫酸銅五水合物、115 ml/1硫酸及75 mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇、50 mg/1之 雙（3-磺丙基）二硫化物二鈉鹽。赫耳電池嵌板利用平均電流 1安培及陽極··陰極電流密度將近2 : 1之脈衝逆電流機制電 鍍1 5分鐘，經計算之厚度比爲2.1 5 : 1。沉積在高電流密度 區爲平滑暗淡的，低電流密度區則爲半明亮的。 實例 1 〇 製備一含有75 g/Ι硫酸銅五水合物、1 1 5 ml/ι硫酸及75 mg/1氯離子之溶液。添加3 0 0 mg/1之聚乙二醇、30 mg/1之 雙（乙烷-2_硫酸鹽）二硫化物二鈉鹽及40 mg/1之商業用調平 -15- 1261075 化合物A。赫耳電池嵌板利用平均電流1安培及陽極：陰極 電流密度將近2 : 1之脈衝逆電流機制電鍍1 5分鐘，經計算 之厚度比爲1 · 7 0 : 1。沉積在高電流密度區爲平滑暗淡的， 低電流密度區則爲全明亮的。 實例1 1 製備一含有75 g/Ι硫酸銅五水合物、1 1 5 ml/ι硫酸及75 mg/l熱離子之溶液。添加300 mg/l之聚乙二醇、30mg/l之 雙（3-磺丙基）二硫化物二鈉鹽及5〇 mg/1之商業用調平化合 _ 物B。赫耳電池嵌板利用平均電流1安培及陽極：陰極電流 密度將近2 : 1之脈衝逆電流機制電鍍1 5分鐘，經計算之厚 度比爲2.2 0 : 1。嵌板表面在高電流密度區爲平滑暗淡的， 低電流密度區則爲全明亮的。 實例 1 2 ' 製備一含有75 g/Ι硫酸銅五水合物、1 15 ml/1硫酸及75 _ mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇、30 mg/1之 雙（3-磺丙基）二硫化物二鈉鹽及40 mg/Ι之商業用調平化合_ 物A。赫耳電池嵌板利用平均電流1安培及陽極：陰極電流 密度將近2 : 1之脈衝逆電流機制電鍍1 5分鐘，隨後施以1 安培直流電5分鐘。經計算之厚度比爲2 . 1 5 : 1。經過全嵌 . 板之沉積爲明亮的。 圖式簡單說明：無The secondary white has a solution of 7 5 g / 1 copper sulfate pentahydrate, 1 1 5 m 1 /1 sulfuric acid and 7 5 llg / 1 chloride ion. 300 mg/1 polyethylene glycol and 3 mg mg/i bis(ethane-2-sulfate) disulphide disodium salt were added. The Hertz cell panel was plated with DC % 1 amp for 15 minutes and the calculated thickness ratio was 4. 〇 : I. The deposition through the entire 1261075 range is semi-bright. Examples 6 - 12 show a non-limiting plating bath of the invention. The composition and plating conditions used in these examples are listed in Tables 2 - 3 below. Table 2. Various Copper Electroplating Baths of the Invention Example 6 Example 7 Example 8 Example 9 Copper sulfate pentahydrate 75 g / 1 75 g / l 75 g / 1 75 g / 1 Sulfuric acid 115 ml / 1 115 ml / 1 115 ml / 1 115 ml/1 chloride ion 75 mg/1 75 mg/1 150 mg/1 150 mg/1 additive 300 mg/1 PAG MacuSpec PPR 300 mg/1 PAG 300 mg/1 PAG additive 30 mg/1 disodium salt2 30 mg/ 1 disodium salt3 50 mg/1 disodium salt3 Electrode type reverse pulse reverse pulse reverse pulse reverse pulse current 1 amp 1 amp 1 amp 1 amp plating time 15 minutes 15 minutes 15 minutes 15 minutes thickness ratio 2.20 : 1 1.9 : 1 2.20 : 1 2.15 : 1 〗 PAG = polyethylene glycol 2 disodium salt = double (birth-2 - sulfuric acid) disulfide disodium salt 3 disodium salt = bis (3 - extended propyl) disulfide disodium salt 1261075 Table 3 Example of various copper electroplating baths of the present invention Example n Example 12 Copper sulfate pentahydrate 75 g/l 75 g/l 75 g/1 Sulfuric acid 115 ml/1 115 ml/1 115 ml/1 Chloride ion 75 mg/l 75 mg/ l ]50 mg/l additive 300 mg/l PAG1 300 mg/l PAG 300 mg/l PAG additive 30 mg/l disodium salt2 30 mg/l disodium salt3 30 mg/l disodium Salt3 additive 40 mg/l leveling compound A 50 mg/l leveling compound B 40 mg/l leveling compound A plating type reverse pulse reverse pulse reverse pulse current 1 amp 1 amp 1 amp plating time 15 minutes 15 minutes 15 minutes thickness Ratio 1.70: 1 2.20 : 1 2.15 : 1 ·· Polyethylene glycol 2 disodium salt = double (B-Yuan-2 - sulfuric acid) monosulfide-sodium salt 3 disodium salt = double (3_propanyl)-sulfide A sodium salt example 6 A solution containing 75 g/inch of copper sulfate pentahydrate, 1 15 ml/1 sulfuric acid, and 75 mg/1 chloride ion was prepared. 300 mg / 1 of polyethylene glycol and 30 mg / 1 of bis (ethane - 2 - sulfate) disulfide disodium salt were added. Hertz battery panels utilize a flat current average of 1 amp and an anode: the cathode current density is nearly 2:1 pulse reversed ~ flow mechanism electroplating for 1 5 minutes' calculated thickness ratio is 2.2 0 ··1. The panels are smooth and dim in the high current density region and semi-bright in the low current density region. Example 7 A solution containing 75 g/t of copper sulfate pentahydrate, 1 15 ml/1 sulfuric acid, and 75 -14-1261075 mg/l chloride ion was prepared. The force is applied to the exclusive augmentation tincture (μ acuSpec PPR, a process used for printed circuit board plating). Hertz cell panels are plated with an average current of 1 amp and an anode: cathode current density of approximately 2:1 for a reverse current mechanism for 15 minutes, with a calculated thickness ratio of 1.9:1. The sinking in the current density region is smooth and dim, and the low current density region is semi-bright. Example 8 * A solution containing 7 5 g / 1 copper sulfate pentahydrate, 1 15 m 1 /1 sulfuric acid and 150 mg / 1 chloride ion was prepared. 300 mg/l of polyethylene glycol and 30 mg/l of bis(3-sulfopropyl) disulphide disodium salt were added. Hertz cell panels were plated with an average current of 1 amp and an anode: cathode current density of approximately 2:1 by a pulsed reverse current mechanism for 15 minutes with a calculated thickness ratio of 2.20:1. The deposition is smooth and dim in the high current density region, and the low current density region is semi-bright. - Example 9 - A solution containing 75 g/t of copper sulfate pentahydrate, 115 ml/1 sulfuric acid and 75 mg/1 chloride ion was prepared. Add 300 mg/1 polyethylene glycol and 50 mg/1 bis(3-sulfopropyl) disulphide disodium salt. The Hertz cell panel is plated with an average current of 1 amp and an anode current of a cathode of approximately 2:1 for a period of 15 minutes with a calculated thickness ratio of 2.1 5:1. The deposition is smooth and dim in the high current density region, and the low current density region is semi-bright. Example 1 制备 A solution containing 75 g/inch of copper sulfate pentahydrate, 1 15 ml/ι sulfuric acid, and 75 mg/1 chloride ion was prepared. Add 300 mg/1 polyethylene glycol, 30 mg/1 bis (ethane-2_sulfate) disulfide disodium salt and 40 mg/1 commercial leveling -15-1261075 Compound A . The Herr cell panel is plated for 1 5 minutes using a pulse current of approximately ampere and an anode: cathode current density of approximately 2:1, and the calculated thickness ratio is 1 · 7 0 : 1. The deposition in the high current density region is smooth and dim, and the low current density region is fully bright. Example 1 1 A solution containing 75 g/t of copper sulfate pentahydrate, 1 15 ml/m sulfuric acid and 75 mg/l of thermionic ion was prepared. 300 mg/l of polyethylene glycol, 30 mg/l of bis(3-sulfopropyl) disulphide disodium salt and 5 〇 mg/1 of commercial leveling compound B were added. The Herr battery panel utilizes an average current of 1 amp and an anode: cathode current density for nearly 5:1 pulsed reverse current mechanism for 15 minutes, with a calculated thickness ratio of 2.2 0:1. The panel surface is smooth and dim in the high current density region, and the low current density region is fully bright. Example 1 2 ' A solution containing 75 g / Ι copper sulfate pentahydrate, 1 15 ml / 1 sulfuric acid and 75 _ mg / 1 chloride ion was prepared. Add 300 mg/1 polyethylene glycol, 30 mg/1 bis(3-sulfopropyl) disulphide disodium salt and 40 mg/Ι commercial leveling compound A. The Herre cell panel utilizes an average current of 1 amp and an anode: cathode current density for approximately 5:1 pulsed reverse current mechanism for 15 minutes, followed by 1 amp DC for 5 minutes. The calculated thickness ratio is 2.15:1. After full embedding, the deposition of the board is bright. Simple description: no